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Insertion reaction of propene into RhH bond in HRh(CO)(PH 3 ) 2 (C 3 H 6 ) compound: A density functional study
Author(s) -
Rocha Willian R.,
De Almeida Wagner B.
Publication year - 2000
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/(sici)1097-461x(2000)78:1<42::aid-qua6>3.0.co;2-f
Subject(s) - propene , chemistry , alkyl , insertion reaction , activation energy , catalysis , regioselectivity , migratory insertion , carbon fibers , reaction mechanism , density functional theory , medicinal chemistry , computational chemistry , organic chemistry , materials science , composite number , composite material
Quantum mechanical calculations at the MP4 (SDQ) level using the BP86‐optimized geometries were carried out to investigate the energies and reaction mechanism for the propene (CH 3 C 1 H CH \documentclass{article}\pagestyle{empty}\begin{document}$^{\mathrm{2}}_{\mathrm{2}}$\end{document} ) insertion reaction into the RhH bond, using the cis ‐HRh(CO)(PH 3 ) 2 compound as a model catalytic species. Since the reaction may occur on the branched carbon 1 or in the normal carbon 2 , which leads to branched and normal Rh(alkyl) compounds, respectively, we investigated these two mechanisms. The results show that the insertion in the branched carbon has an activation energy of 16.2 kcal/mol, and the activation energy for the reaction to take place at the normal carbon is 14.3 kcal/mol. These activation energies, together with the calculated relative energy of the metal–alkyl compounds formed after the insertion considering these two pathways, were used to access the regioselectivity on this reaction. We found a ratio of normal‐ and iso‐products, n :iso, of (96:4), which is in excellent agreement with the experimental regioselectity of (95:5). © 2000 John Wiley & Sons, Inc. Int J Quant Chem 78: 42–51, 2000